KR101917355B1 - Manufacturing method of eco-friendly releasing agent - Google Patents

Abstract

The present invention relates to an environmentally friendly release agent composition, an environmentally friendly release agent, and a manufacturing method thereof, and more specifically, to an environmentally friendly release agent, which has a significantly reduced risk of fire without the use of solvents including benzene, which is a harmful component of the human body, a composition used in the manufacture of the releasing agent and a method for manufacturing the releasing agent using the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a manufacturing method of a releasing agent for a polyurethane molded foam,

The present invention relates to a releasing agent used in a polyurethane molding foam, a composition used therefor, and a method for producing an environmentally friendly releasing agent using the same.

In order to obtain a molded foam made of resin or rubber, a mold is filled with a resin or a rubber material and molding is carried out. Usually, the external mold release agent is previously applied to the mold before charging. Examples of the external releasing agent include waxes such as paraffin wax and polyethylene wax, silicones such as polydimethylsiloxane oil and silicone oil, organic compounds such as glycol, fatty acid derivatives and perfluoroalkyl group-containing compounds, oils such as talc and mica, Compound or the like is dispersed or dissolved in water or an organic solvent.
These external mold release agents are usually applied each time and used. However, in order to reduce the number of process steps in terms of workability, development of a mold release agent having an extended mold release life is desired. Also, there is a problem of contamination of the mold due to the deposition of the outer mold agent due to the application each time, and particularly, the wax type mold release agent is severely contaminated. This is because the release agent is basically required to be partially coated on the side of the molding foam. This is because of the poor finish such as sticking of the molding foam, poor coating on the molding foam in the subsequent process, As a cause, cleaning with an organic solvent such as trichloroethane is performed after molding. Particularly, the silicone-based releasing agent is liable to cause poor coating and poor adhesion.
Another way to facilitate release is to use an internal release agent (IMRA). IMRA is a surface active additive in resin formulations that is typically transferable from the resin volume to the resin / mold interface. Since IMRA is incorporated into the formulation, it is not necessary to apply the external mold on the mold surface repeatedly. After molding, IMRA reduces adhesion of the molded article from the mold to facilitate separation of the molded article from the mold.
Research has been conducted for decades to find an effective IMRA for polyurethanes. Previously, fatty acid derivatives, esters, metal soaps, organic salts and siloxane / silicone have been tried as polyurethane IMRA. However, when manufacturing a conventional IMRA, a solvent containing a harmful component such as benzene, toluene, and xylene is used, and the existing IMRA has a problem of fire due to a low flash point.

Korean Patent Publication No. 10-2015-0121063 (Publication date October 28, 2015)

The present invention has been accomplished after many experiments and studies for solving the problems and necessity as described above. The present inventor has found that the present invention can reduce the solid content per the same area in the release agent as compared with the conventional release agent, A release agent using the same, and a process for producing the same.

In order to solve the above problems, the release agent composition for a polyurethane mold form of the present invention includes wax, a catalyst, a corrosion inhibitor, a dispersion aid, a polyurethane cell stabilizer and a non-aromatic refined petroleum solvent.
Another object of the present invention is to provide a release agent for a polyurethane molded foam produced using the above composition.
It is still another object of the present invention to provide a method for producing a release agent for a polyurethane molded foam using the composition.

The release agent for a polyurethane molding foam of the present invention does not use an aromatic solvent containing harmful components in a human body such as benzene, toluene, and xylene, and has less application amount than conventional release agents, In addition, since it has a boiling point of 70 ° C or higher, it can reduce the risk of fire that may occur during use and storage.

실험예 1 : 이형제의 물성 측정
상기 실시예 및 비교예에서 제조한 이형제의 인화점, 점도, 비중, 고형분 함량을 하기 방법으로 측정하였고, 그 결과를 하기 표 2에 나타내었다.
(1) 인화점 측정
KS M ISO 3679 시험방법에 의거하여 측정하였다.
(2) 점도 측정
KS A 0531 시험방법에 의거하여 측정하였다.
(3) 비중 측정
KS A 0601 시험방법에 의거하여 측정하였다.
(4) 고형분 함량 측정
KS M ISO 3251 시험방법에 의거하여 측정하였다.

상기 표 2를 살펴보면, 실시예 및 비교예 모두 인화점이 70℃ 이상을 보였다.
파라핀왁스 적게 사용한 비교예 1의 경우, 실시예와 비교할 때 점도가 낮은 문제가 있었으며, 파라핀왁스를 너무 많이 사용한 비교예 2의 경우, 점도가 높은 문제가 있었다. 또한, 왁스 자체를 5 중량% 미만으로 적게 사용한 비교예 3 및 촉매 사용량이 너무 적었던 비교예 5의 경우, 이형제의 점도가 너무 낮은 문제가 있었고, 왁스 자체를 15 중량% 초과하여 사용한 비교예 4 및 촉매 사용량이 너무 많았던 비교예 6의 경우, 점도가 너무 높은 문제가 있었다.
또한, 부식방지제 함량이 1 중량%를 초과한 비교예 7 및 분산보조제 함량이 1 중량%를 초과한 비교예 8의 경우, 실시예 1과 비교할 때, 점도, 고형분 함량뿐만 아니라, 비중도 상대적으로 높은 문제가 있었다.
그리고, 폴리우레탄 셀 안정제를 0.01 중량%를 미만으로 사용한 비교예 9 및 폴리우레탄 셀 안정제를 0.5 중량% 초과하여 사용한 비교예 10의 경우, 인화점이 70℃ 미만으로 낮았으며, 비교예 10의 경우, 점도가 낮으면서 고형분 함량이 높은 문제가 있었다.
상기 실시예 및 실험예를 통하여, 본 발명이 이형제 내 동일 면적 당 고형분 함량을 줄이면서도, 톨루엔 등의 유해 성분을 사용하지 않는 친환경적인 이형제를 제공할 수 있음을 확인할 수 있었다.Hereinafter, the present invention will be described more specifically.
The release agent for the polyurethane foam of the present invention is prepared using a release agent composition comprising a wax, a catalyst, a corrosion inhibitor, a dispersion aid, a polyurethane cell stabilizer and a non-aromatic refined petroleum solvent.
The wax of the release agent composition component may comprise at least one member selected from the group consisting of polyethylene wax and paraffin wax, preferably polyethylene wax and paraffin wax at a weight ratio of 1: 0.15 to 0.35, more preferably polyethylene Wax and paraffin wax may be mixed at a weight ratio of 1: 0.18 to 0.28. If the paraffin wax content ratio is less than 0.15 weight ratio, coating and releasing effects due to mixing may be insufficient. If the paraffin wax content exceeds 0.35 weight ratio, the cell stability of the polyurethane foam may deteriorate.
The content of the wax in the total weight of the composition is 5 to 15 wt%, preferably 6.5 to 12 wt%, more preferably 7.5 to 10 wt%. When the content of the wax in the total weight of the composition is less than 5 wt% There may be a problem that the cell stability and releasability of the polyurethane molded foam is poor, and if it exceeds 15% by weight, there is a problem that buildup is difficult due to poor application. That is, when the mold is continuously operated, the mold release agent is remained on the surface of the mold except for the volatile solvent and other additives, and the skin surface becomes irregular, so it is necessary to periodically clean the mold. In this case, when the excessive amount of wax is not used, the amount of wax accumulated in the molding mold is increased so that the cleaning cycle of the mold is accelerated, and the wax particles are irregularly formed on the appearance of the finished molded foam, have.
The above catalysts in the components of the mold release agent complement the curing promotion and releasability of the polyurethane molded foam. The catalysts can be selected from common catalysts used in the art, such as DBTDL (Dibutyltin dilaurate), DOTL (Dioctyltin dilaurate) , DBTO (Dibutyltin Oxide), and DOTO (Dioctyltin Oxide). The catalyst may be used in an amount of 0.05 to 2% by weight, preferably 0.1 to 1% by weight, more preferably 0.2 to 0.6% by weight, based on the total weight of the composition. There may be a problem of promoting the hardening of the back side and releasing property. When the amount of the catalyst is more than 2% by weight, there is a problem of appearance of the polyurethane molded foam produced.
The anticorrosive agent of the mold release agent composition component serves to prevent corrosion of the mold. The anticorrosion agent may be a conventional anticorrosion agent used in the art, preferably stearylamine, octadecylamine, Glycerol and benzotriazole may be used. The amount of the corrosion inhibitor to be used may be 0.1 to 1% by weight, preferably 0.1 to 0.8% by weight, more preferably 0.2 to 0.5% by weight, based on the total weight of the composition. %, Corrosion of the mold may occur, and when the amount of the corrosion inhibitor is more than 1% by weight, there is a problem of quality in which a large amount of fine particles are generated.
The dispersing aid in the releasing agent composition component serves to improve the dispersibility of the corrosion inhibitor in the composition. The dispersing aid may be an ordinary dispersing aid used in the art, preferably an alkane carboxylate, a cyclohexanone acid, Treated mullite wax and calcium stearate may be used. The amount of the dispersing aid to be used may be 0.1 to 1% by weight, preferably 0.1 to 0.8% by weight, more preferably 0.1 to 0.5% by weight, based on the total weight of the composition. %, There is a problem of cell open failure of the polyurethane molded foam.
Among the components of the release agent composition, the polyurethane cell stabilizer plays a role of stabilizing the skin of the polyurethane molded foam, that is, stabilizing the polyurethane cell, and may use a general polyurethane cell stabilizer used in the art , Preferably at least one selected from polyether modified with polysiloxane, polydimethylsiloxane, and organofunctional polydimethylsiloxane can be used. The amount of the polyurethane cell stabilizer may be 0.01 to 0.5% by weight, preferably 0.05 to 0.3% by weight, more preferably 0.08 to 0.25% by weight based on the total weight of the composition. If the amount is less than 0.01% by weight, the stability of the polyurethane cell may deteriorate. If the amount of the polyurethane cell stabilizer is more than 0.5% by weight, the cell particles may be small, and deformation may be caused.
As the refining petroleum solvent for use in the mold release agent composition component, a non-aromatic solvent may be used, and preferably a non-aromatic refined petroleum solvent having a flash point of 70 ° C or higher is preferably used. As the non-aromatic refined petroleum solvent, preferably at least one selected from the group consisting of hydrogenated hard refined oil and hydrogenated heavy naphtha can be used. The amount of the refined petroleum solvent is used in the total weight of the composition by weight percent of the remaining amount excluding the wax, the catalyst, the corrosion inhibitor, the dispersion aid, and the polyurethane cell stabilizer.
The eco-friendly releasing agent of the present invention can be produced by adding wax, a corrosion inhibitor and a dispersing aid to a non-aromatic refined petroleum solvent, stirring and dissolving the wax, dissolving the wax A step of preparing a liquid; A second step of adding a polyurethane cell stabilizer, a catalyst and the wax solution to a tank mixer to which a non-aromatic refined petroleum solvent is added in order, followed by simultaneous stirring and reaction with a homomixer and a paddle to prepare a reaction solution; Cooling the reaction solution by adding cooling water while paddling the reaction solution; And a fourth step of filtering the cooled reaction solution.
In the first step, the stirring is preferably performed at 95 to 120 ° C, preferably at 95 to 110 ° C, more preferably at 98 to 105 ° C. If the temperature is less than 95 ° C, There may be a problem that the dissolving time is too long, and when it exceeds 120 ° C, there is a problem that the working time is unnecessarily prolonged.
In the second step, the agitation is advantageously carried out with homomixer and paddle under 2,000 to 4,000 rpm, preferably 2,500 to 3,500 rpm, more preferably 2,500 to 3,000 rpm, in terms of uniform stirring and low viscosity.
Then, in step 2, the reaction is allowed to proceed for 40 to 50 minutes, preferably 42 to 47 minutes, more preferably 43 to 46 minutes, by stirring the homomixer and the paddle simultaneously with stirring. In this case, the reaction solution in the second step refers to a solution containing the reaction products in the two steps and the like.
When the third step is completed, the reaction is carried out by paddle stirring and additional reaction, then cooling water is added to lower the temperature to 24 ° C or lower, preferably 15-24 ° C, more preferably 16-20 ° C, . At this time, the cooled reaction solution means a solution containing three reaction products and the like.
The four-step filtering is to remove the unnecessary solid components and impurities in the cooled reaction solution and to obtain the eco-friendly release agent of the present invention which is the final reaction product, and a general filtering method used in the art can be used.
The environmentally friendly releasing agent for a polyurethane molded foam of the present invention thus produced may have a flash point of 70 ° C or higher, preferably 70-75 ° C, and more preferably 70-73.5 ° C.
Further, the environmentally friendly releasing agent for a polyurethane molded foam of the present invention may have a viscosity at 25 ° C of 112 to 140 cps, preferably 115 to 138 cps, more preferably 120 to 136 cps.
The eco-friendly release agent for a polyurethane molded foam of the present invention may have a specific gravity of 0.750 to 0.850, preferably a specific gravity of 0.770 to 0.830, more preferably 0.780 to 0.815.
The eco-friendly release agent for a polyurethane molded foam of the present invention may have a boiling point of 200 to 300 캜, preferably 200 to 250 캜.
The eco-friendly release agent for a polyurethane molded foam of the present invention has a very large solid content of 6 to 10% by weight, more preferably 7.5 to 10% by weight, and still more preferably 8.2 to 9.8% by weight, based on the total weight of the release agent .
Such an environmentally friendly releasing agent for a polyurethane molded foam of the present invention can preferably be used as an external releasing agent of a polyurethane molded foam.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
[Example]
Example 1: Preparation of eco-friendly release agent for polyurethane foam
Polyethylene wax and paraffin wax were mixed at a weight ratio of 1: 0.15 to 0.35 to prepare a mixed wax. Then, the mixed wax, the stearylamine (corrosion inhibitor) and the alkane carboxylate (dispersion auxiliary) were added to the non-aromatic refined petroleum solvent, the temperature was raised to 100 ° C, And dissolved to prepare a wax dissolving solution.
Next, a polysulfone-modified polyether (polyurethane cell stabilizer) and DBTDL (catalyst) were fed into a tank mixer to which a non-aromatic refined petroleum solvent was added, and then the wax solution was added. Next, the mixture was stirred and reacted with a homomixer and a paddle at 100 占 폚 or lower for 45 minutes at the same time and reacted to prepare a reaction solution containing the reaction product.
Next, the reaction solution was stirred with Pheld stirring and further reacted, and then cooling water was added and stirred to prepare a cooled reaction solution at 20 to 21 ° C.
Next, the cooled reaction solution was filtered and filtered to prepare an environmentally friendly release agent for a polyurethane molded foam. The composition ratios of the compositions used in the production are shown in Table 1 below.
Examples 2 to 5 and Comparative Examples 1 to 10
A release agent was prepared in the same manner as in Example 1, except that each of the release agents was prepared so as to have the composition ratios shown in Table 1 below, and Examples 2 to 5 and Comparative Examples 1 to 10 were conducted.

Experimental Example 1: Measurement of physical properties of a release agent
The flash point, viscosity, specific gravity, and solid content of the release agent prepared in Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.
(1) Flash point measurement
Measured according to KS M ISO 3679 test method.
(2) Viscosity measurement
It was measured according to the KS A 0531 test method.
(3) Density measurement
It was measured according to the KS A 0601 test method.
(4) Measurement of solid content
Measured according to KS M ISO 3251 test method.

Referring to Table 2, the flash point of each of Examples and Comparative Examples was 70 ° C or more.
In the case of Comparative Example 1 in which paraffin wax was less used, there was a problem in that the viscosity was lower than that in Examples, and in Comparative Example 2 in which paraffin wax was used in excess, there was a problem of high viscosity. In Comparative Example 3 in which the wax itself was used in an amount of less than 5% by weight and Comparative Example 5 in which the amount of catalyst was too small, there was a problem that the viscosity of the releasing agent was too low. In Comparative Example 4 And Comparative Example 6 in which the amount of catalyst used was too large, there was a problem that the viscosity was too high.
In the case of Comparative Example 7 in which the content of the corrosion inhibitor exceeded 1% by weight and Comparative Example 8 in which the content of the dispersing aid exceeded 1% by weight, the viscosity and the solid content as well as the specific gravity There was a high problem.
In Comparative Example 9 using less than 0.01% by weight of the polyurethane cell stabilizer and Comparative Example 10 using more than 0.5% by weight of the polyurethane cell stabilizer, the flash point was lower than 70 占 폚. In Comparative Example 10, There was a problem that the solid content was high while the viscosity was low.
Through the above Examples and Experimental Examples, it was confirmed that the present invention can provide an environmentally friendly release agent that does not use harmful components such as toluene while reducing the solid content per the same area in the release agent.

Claims (9)

delete delete delete delete Adding a wax, a corrosion inhibitor and a dispersion aid to a non-aromatic refined petroleum solvent having a flash point of 70 ° C or higher, and then stirring and dissolving at 95 to 120 ° C to prepare a wax solution;
The polyurethane cell stabilizer, the catalyst and the wax solution were put into a tank mixer to which a non-aromatic refining petroleum solvent was added, and the mixture was stirred simultaneously with homomixer and paddle at a stirring speed of 2,000 to 4,000 rpm for 40 to 50 minutes (2) a step of preparing a reaction solution by performing a reaction;
Stirring the reaction solution by paddle and further reaction, and then cooling the reaction solution to 24 캜 or lower by the addition of cooling water; And
And filtering the cooled reaction solution,
The reaction liquid in the second step is a mixture of 5 to 15 wt% of wax, 0.05 to 2 wt% of catalyst, 0.1 to 1 wt% of corrosion inhibitor, 0.1 to 1 wt% of dispersion aid, 0.01 to 0.5 wt% of polyurethane cell stabilizer, Aromatic refining petroleum solvent,
Wherein the wax comprises polyethylene wax and paraffin wax at a weight ratio of 1: 0.15 to 0.35,
The release agent prepared by the 4-step process has a solid content of 7.5 to 10% by weight in the total weight of the release agent,
Wherein the releasing agent has a flash point of 70 to 75 DEG C, a viscosity at 25 DEG C of 115 to 138 cps, a specific gravity of 0.770 to 0.830, and a boiling point of 200 to 250 DEG C. delete delete delete delete